The ICN photodissociation reaction is the prototype system for understanding energy disposal and curve crossing in small molecule bond-breaking. The wide knowledge base on this reaction in the gas phase makes it an excellent test case to explore and understand the influence of a liquid solvent on the photo-induced reaction dynamics. Molecular dynamics simulations that include surface-hopping have addressed numerous aspects of how the solvent should influence non-adiabatic transitions and energy flow and ultimately determine product branching for this reaction system. In this paper, we report femtosecond transient absorption work directly combined with new molecular dynamics simulations that make direct connection with the spectroscopic observables. The full spectral evolution after initiating ICN photodissociation at 266 nm in water and ethanol is recorded with unprecedented time resolution, fast enough to see the nascent products emerge before interacting with the solvent cage. Use of a 266 nm pump maximizes the probability of subsequent caging on the upper diabat while launching large rotational energy release for trajectories emerging on the lower diabat. The 2D dataset yields a map of the different products and how they interconvert. In particular, information on the branching ratio and spectral evolution of the product bands is revealed as the products relax their electronic and rotational degrees of freedom. An evolution from rotationally hot gas-phase like CN (sharp band, at 390 nm) to equilibrated and solvated CN radicals (broad, at 326 nm in water and 415 nm in ethanol) is clearly observed in both solvents, and signals assignable to I* are also captured. The non-adiabatic molecular dynamics simulations focus on identifying when trajectories curve cross, filtering the trajectory ensemble into spectroscopically distinct sub-populations and analyzing the rotational energy for the CN product population. The experimental results, taken together with the MD simulations, establish the initial surface crossing probability and suggest multiple passes through the curve crossing region determine the final product yields and provide a source of freshly torqued CN radicals that continues to top up the population of rotationally hot photoproduct over the first few picoseconds.